Multi-layer effect pigment

ABSTRACT

A multilayer effect pigment includes a transparent substrate, a layer of high refractive index material on the substrate, and alternating layers of low refractive index and high refractive index materials on the first layer, the total number of layers being an odd number of at least three, all adjacent layers differing in refractive index by at least about 0.2 and at least one of the layers having an optical thickness which is different from all of the other layers. The resulting multilayer effect pigment is not a quarter-wave stack. The present effect pigments may be used in cosmetic and industrial applications.

This application is a continuation-in-part of U.S. Ser. No. 10/346,076,filed Jan. 17, 2003.

BACKGROUND OF THE INVENTION

Effect pigments, also known as pearlescent or nacreous pigments, arebased on the use of a laminar substrate such as mica or glass flakewhich has been coated with a metal oxide layer. These pigments exhibitpearl-like luster as a result of reflection and refraction of light, anddepending on the thickness of the metal oxide layer, they can alsoexhibit interference color effects.

Titanium dioxide-coated mica and iron oxide-coated mica effect pigmentsare the effect pigments which are encountered most often on a commercialbasis. Pigments in which the metal oxide has been over-coated withanother material are also well known in the art.

The commercially available effect pigments which contain only a singlecoating of a high refractive index material provide only two reflectinginterfaces between materials. These two material interfaces (andreflections) are therefore solely responsible for the reflectivityachieved from the platelet surface. A substantial percentage of theincident light is thus transmitted through the platelet and while thisis necessary to create the nacreous appearance of the pigment, it alsodiminishes other desirable properties of the effect pigments such asluster, chromaticity and hiding power. To counteract this consequence,the art has either mixed the effect pigments with other pigments oradded additional layers of transparent and/or selectively absorbingmaterials onto the effect pigment.

Examples of prior art describing multi-coated effect pigments include JP7-246366, WO 98/53011, WO 98/53012 and U.S. Pat. No. 4,434,010. All ofsuch prior art requires that each coated layer possess an opticalthickness equal to a whole number multiple of a one-quarter of thewave-length at which interference is expected. Such construction of theso-called quarter-wave stacks is a widely accepted and implementedcondition in the thin-film industries. Because of this limitation, aunique layer thickness combination is essential in order to create eachindividual one of the interference colors of the visible spectrum. Thebase substrate is the only dimension common to all of the compositionsdisplaying different interference colors.

It has now been discovered that the adherence to the quarter-wave stackapproach is unnecessary and suitable products, even with substantialgains in luster, chromaticity and hiding power, can be achieved withoutobserving that requirement. Further, numerous other advantages can berealized.

It is accordingly the object of this invention to provide a newmulti-layer effect pigment, including having improved luster,chromaticity and/or hiding power relative to other effect pigments.

SUMMARY OF THE INVENTION

This invention relates to a multi-layer effect pigment and moreparticularly, to a multi-layer effect pigment which includes atransparent substrate having a transparent high refractive indexmaterial layer thereon and at least one pair of layers which are atransparent high refractive index material and a transparent lowrefractive index material, in which the total number of layers is an oddnumber, in which every two adjacent non-substrate layers differ inrefractive index by at least about 0.2 and in which at least one layerhas an optical thickness which is different from all of the otherlayers, whereby the pigment is not a quarter-wave stack.

The present invention provides a multilayer effect pigment comprising: atransparent substrate having a first layer of titanium dioxide thereon,the first layer having a thickness of about 35 to 160 nm, a second layerof a low refractive index material on the first layer and an outermostlayer of a high refractive index material placed on the second layer,the high refractive index material comprises titanium dioxide having athickness of from about 20 to 175 nm and the low refractive indexmaterial is silicon dioxide having a thickness of about 20 to 80 nm, andwherein at least one layer has an optical thickness which is differentfrom all of the other layers, whereby the pigment is not a quarter-wavestack.

DESCRIPTION OF THE INVENTION

In accordance with the present invention, the effect pigment is amulti-layered product composed of a transparent substrate having an oddnumber of layers thereon and in which at least one of the layers has anoptical thickness which is different from all of the other layerscausing the pigment not to be a quarter-wave stack.

Any encapsulatable smooth and transparent platelet can be used as thesubstrate in the present invention. Examples of useable plateletsinclude mica, whether natural or synthetic, kaolin, glass flakes and thelike. The substrate need not be totally transparent but should,preferably, have at least about 75% transmission. The size of theplatelet shaped substrate is not critical per se and can be adapted tothe particular use. Generally, the particles have largest majordimensions averaging about 5-250 microns, preferably 5-100 microns, andan aspect ratio greater than about 5. Their specific free surface area(BET) is, in general, from about 0.2 to 25 m²/g.

The layers encapsulating the substrate alternate between high refractiveindex materials and low refractive index materials. The high refractiveindex materials can be anatase titanium dioxide, rutiletitanium:dioxide, iron oxide, zirconium dioxide, zinc oxide, zincsulfide, bismuth oxychloride or the like. The low refractive indexmaterial can be silicon dioxide, magnesium fluoride, aluminum oxide, apolymer such as polymethyl methacrylate, polystyrene, ethylene vinylacetate, polyurea, polyurethane, polydivinyl benzene and the like. Anycombination of materials can be selected provided that adjacent layersdiffer in refractive index by at least about 0.2, and more preferably atleast about 0.6. The materials are transparent but may, like iron oxideand chromium oxide, have an absorption component.

The individual layers can be applied to the substrate and to each otherusing techniques well known in the art. Any such technique can beutilized. One of the advantages of the invention is that sol-geltechniques can be used to apply the coatings. Such techniques are wellknown and widely practiced for thin film deposition, and are safe,economical and amenable to a wide variety of particle shapes and sizes.Chemical vapor deposition techniques which have been used in some priorart have a litany of negative aspects including safety hazards,expensive reagents and infrastructure and substrate particle sizelimitations. Monolithic web-based multi-layer coating techniques havealso been used in the prior art and suffer from the disadvantages thatpigment particles are formed after the coatings are applied andtherefore have discontinuities in the layers at the fracture points. Theparticles must also be classified according to size after the monolithis fractured, whereas in the present invention the particle size can bepredetermined before the coating and can be constant.

Another advantage of the present invention is that the substrate and alllayers have an appreciable degree of transparency and therefore theresulting pigments can exhibit unique angle dependent reflectivityranging from nearly totally reflecting to substantially transmitting asthe viewing angle is changed. Many multi-coated pigments in the priorart use metal flakes as substrates and such metal layers are not capableof transmitting light and the resulting pigment is therefore totallyopaque.

Because the pigment is not a quarter-wave stack, the first layer whichis adjacent the substrate can be given a fixed thickness and by varyingthe thickness of the other layers, it is possible to prepare all of theinterference colors desired.

While any odd number of layers equal to or greater than three can beemployed, it has been found that substantial advantages are present whenthere are three layers and this is therefore preferred.

The low refractive index is preferably silica and while this can haveother thicknesses, the silica layer preferably has a thickness in therange of about 20-80 nm, and more preferably about 40-80 nm. Thisminimizes the degree of angle dependent color travel, which is inherentin silica films. Silica layers which have a thickness greater than 80nanometers produce a wider range of angle dependent colors which is notalways desirable.

The first layer on the substrate and the outermost layer can be the sameor different, but are preferably the same, and are further preferablytitanium dioxide. It will be appreciated that where the first orinnermost layer has a fixed thickness and the low refractive index layeralso has a predetermined thickness, the outermost high refractive indexlayer will control the interference color as a result of its thickness.The substrate/first layer/second layer combination thus acts as auniversal base from which all interference colors can be realized bysimply varying the thickness of the third layer. The thickness of thethird layer, when it is titania, in such an arrangement generally variesfrom about 20 to 250 nm, and preferably about 60-175 nm. Preferably, thefirst layer will have a thickness of from about 35 to 160 nm.

While the approach of using a universal substrate/first layer/secondlayer base yields products superior to single-layer TiO₂-coatedsubstrates, optimum pigments of this invention can be derived byemploying a variety of unique thickness combinations. Examples of suchproducts are provided in Table 2 below.

It is further part of the present invention that the pigments have firstand outermost layers which have different thicknesses from each otherand still yield the unexpected color which has been achieved by thesematerials which do not follow the standard quarter-wave theory.Moreover, the TiO₂ layers may have the same thickness. In such case, itis the optical thickness of the low refractive index layer, e.g., SiO₂,which provides the non-quarter wave stack. The most useful pigments ofthis invention will have a chromacity (0° C.*) of at least 40.0.

The products of the present invention can be used in any applicationwhere pearlescent pigments have been used heretofore. Thus, the productsof this invention have an unlimited use in all types of automotive andindustrial paint applications, especially in the organic color coatingand inks field where deep color intensity is required. For example,these pigments can be used in mass tone or as styling agents to spraypaint all types of automotive and non-automotive vehicles. Similarly,they can be used on all clay/formica/wood/glass/metal/enamel/ceramic andnon-porous or porous surfaces. The pigments can be used in powdercoating compositions. They can be incorporated into plastic articlesgeared for the toy industry or the home. These pigments can beimpregnated into fibers to impart new and esthetic coloring to clothesand carpeting. They can be used to improve the look of shoes, rubber andvinyl/marble flooring, vinyl siding, and all other vinyl products. Inaddition, these colors can be used in all types of modeling hobbies.

The above-mentioned compositions in which the compositions of thisinvention are useful are well known to those of ordinary skill in theart. Examples include printing inks, nail enamels, lacquers,thermoplastic and thermosetting materials, natural resins and syntheticresins. Some non-limiting examples include polystyrene and its mixedpolymers, polyolefins, in particular, polyethylene and polypropylene,polyacrylic compounds, polyvinyl compounds, for example polyvinylchloride and polyvinyl acetate, polyesters and rubber, and alsofilaments made of viscose and cellulose ethers, cellulose esters,polyamides, polyurethanes, polyesters, for example polyglycolterephthalates, and polyacrylonitrile.

For a well-rounded introduction to a variety of pigment applications,see Temple C. Patton, editor, The Pigment Handbook, volume II,Applications and Markets, John Wiley and Sons, New York (1973). Inaddition, see for example, with regard to ink: R. H. Leach, editor, ThePrinting Ink Manual, Fourth Edition, Van Nostrand Reinhold(International) Co. Ltd., London (1988), particularly pages 282-591;with regard to paints: C. H. Hare, Protective Coatings, TechnologyPublishing Co., Pittsburgh (1994), particularly pages 63-288. Theforegoing references are hereby incorporated by reference herein fortheir teachings of ink, paint and plastic compositions, formulations andvehicles in which the compositions of this invention may be usedincluding amounts of colorants. For example, the pigment may be used ata level of 10 to 15% in an offset lithographic ink, with the remainderbeing a vehicle containing gelled and ungelled hydrocarbon resins, alkydresins, wax compounds and aliphatic solvent. The pigment may also beused, for example, at a level of 1 to 10% in an automotive paintformulation along with other pigments which may include titaniumdioxide, acrylic lattices, coalescing agents, water or solvents. Thepigment may also be used, for example, at a level of 20 to 30% in aplastic color concentrate in polyethylene.

In the cosmetic and personal care field, these pigments can be used inthe eye area and in all external and rinse-off applications. They arerestricted only for the lip area. Thus, they can be used in hair sprays,face powder, leg-makeup, insect repellent lotion, mascara cake/cream,nail enamel, nail enamel remover, perfume lotion, and shampoos of alltypes (gel or liquid). In addition, they can be used in shaving cream(concentrate for aerosol, brushless, lathering), skin glosser stick,skin makeup, hair groom, eye shadow (liquid, pomade, powder, stick,pressed or cream), eye liner, cologne stick, cologne, cologne emollient,bubble bath, body lotion (moisturizing, cleansing, analgesic,astringent), after shave lotion, after bath milk and sunscreen lotion.

The present effect pigments may also be used in combination with food orbeverages or to coat foods.

In order to further illustrate the invention, various examples are setforth below. In these examples, as well as throughout this specificationand claims, all parts and percentages are by weight and all temperaturesare in degrees Centigrade, unless otherwise indicated.

EXAMPLE 1

Into a 1 liter Morton flask is added a solution of 420 ml ofisopropanol, 32 ml of distilled water and 4 ml of a 29% NH₄OH aqueoussolution. To this stirred solution is added 300 grams of a whitereflecting TiO₂ coated glass flake powder (G130L, REFLECKS™ Pinpoints ofPearl, Engelhard Corporation). The resulting suspension is stirred andheated to 60° C.

A charge of 33.2 grams of tetraethoxysilane is added to the suspension,which is stirred for 18 hours. The suspension is then vacuum filtered,and the presscake dried in a 120° C. oven for 16 hours. The yield of thedried product is 307.4 grams, and the bulk color is a weak red which isnot visible in the reaction suspension.

Into a 2 liter Morton flask equipped with heating, stirring, andtemperature control is added 550 ml of demineralized water and 278 gramsof silica coated intermediate prepared above. The stirring suspension pHis adjusted to 1.5, and the temperature set at 79° C. While maintainingthe pH at 1.5, 16.7 grams of an 18% SnCl₄5H₂O solution is added at aconstant rate over 60 minutes, and then the suspension is stirred at thetemperature and pH set points for 30 minutes beyond the addition. Whilemaintaining the pH at 1.5, and the temperature at 79° C., 50 ml of a 40%TiCl₄ aqueous solution is then added over 60 minutes. The suspension isfiltered, and the presscake rinsed with water and dried for 16 hours at120° C. The yield of final product is 315 grams.

A small portion (5 grams) of the final TiO₂ coated product is calcinedat 600° C. for 20 minutes. Both the 120° C. dried product and the 600°C. calcined product is compared to the singly coated starting material(G130L, Engelhard Corporation) as drawdowns of 12% powder innitrocellulose lacquer. The reflectivity of all the samples is evaluatedboth visually and instrumentally. A large increase in the reflectivityis imparted to the G130L starting material by the application of the 2additional coatings.

EXAMPLE 2

Into a 2 liter Morton flask is added a solution of 900 ml ofisopropanol, 190 ml of distilled water, and 17 ml of a 29% NH₄OH aqueoussolution. To this stirred solution is added 300 grams of a whitereflecting TiO₂ coated mica powder (TIMICA® sparkle, 110P, EngelhardCorporation).

A charge of 176.8 grams of tetraethoxysilane is added to the 60° C.suspension, which is stirred for 18 hours. The suspension is then vacuumfiltered, and the presscake dried at 120° C. for 16 hours. The yield ofsilica coated product is 355 grams. The material displays a weak redreflection color in bulk form, which is not visible in the reactionsuspension.

Into a 3 liter Morton flask equipped with heating, stirring, andtemperature control is added 1000 ml of demineralized water and 150grams of the silica coated intermediate obtained from the previouscoating procedure. While stirring at a constant rate, the suspension isheated to the 74° C. set point, and the pH was adjusted to 1.6. Next,23.5 grams of an 18% SnCl₄5H₂O solution is pumped into the suspensionover 15 minutes while maintaining the pH at 1.6. The suspension isallowed to stir for 30 minutes following the addition.

While maintaining the temperature, stirring rate and pH of thesuspension at the values for the previous reagent addition, an aqueoussolution of 40% TiCl₄ is added to the suspension at a rate of 0.65 mlper minute. During the addition, small aliquots of the suspension getspread onto a black glass plate to monitor the luster and color of thepigment platelets. After 100 ml of TiCl₄ solution is added, there isstill no increase in the luster of the particles, the addition isterminated, and the suspension filtered and the product dried at 120° C.The yield of product is 170 grams. The product is compared to the singlycoated starting material (Timica Sparkle) as a drawdown of 3% pigment innitrocellulose lacquer. The dried paint displays inferior luster to thestarting material, and severe particle agglomeration.

EXAMPLE 3

A slurry of 420 grams of iron oxide coated borosilicate flake (G270L,REFLECKS™ Blazing Bronze, Engelhard Corporation), 590 mls. ofisopropanol, 45 mls. of water, and 5.6 mls. of 29% NH₄OH solution isheated to 60° C. and stirred in a reaction vessel. Then, 46.5 grams oftetraethoxysilane is added to the slurry and stirred at that temperaturefor 20 hours. The slurry is vacuum-filtered and the product dried for 24hours at 135° C., yielding 432.2 grams. A slurry of 416 grams of theaforementioned silica coated product in 756 mls. of water is stirred ina reaction vessel and heated to 79° C. The slurry pH is adjusted to 1.5.An aqueous solution containing 8.93 grams of SnCl₄5H₂O is pumped intothe slurry over a 2 hour period while maintaining the pH at 1.5 with 10%Na₂CO₃ solution. After the addition is completed, the slurry temperatureis raised to 82° C. and the pH is adjusted to 3.0 with 10% Na₂CO₃solution. An aqueous 39% FeCl₃ solution is pumped in at 0.4 g/min whilecontrolling the pH at 3.0 with the 10% Na₂CO₃ solution. The addition isstopped after 81.8 grams of the iron solution is added, and the slurryis then vacuum-filtered, the presscake washed with water, and thencalcined for 90 minutes at 650° C.

Both the calcined product and base iron oxide-coated glass flake arecompared as drawdowns of 12% powder in nitrocellulose lacquer. Thecalcined product is seen to exhibit a bronze shade with superiorreflectivity and chromaticity to that of the base material.

EXAMPLE 4

A slurry of 420 grams of titanium dioxide coated borosilicate flake(G130L, REFLECKS™ Pinpoints of Pearl, Engelhard Corporation), 590 mls.of isopropanol, 45 mls. of water, and 5.6 mls. of 29% NH₄OH solution isheated to 60° C. and stirred in a reaction vessel. Then, 46.5 grams oftetraethoxysilane is added to the slurry and stirred at that temperaturefor 20 hours. The slurry is vacuum-filtered and the product dried for 24hours at 135° C., yielding 432.2 grams. A slurry is prepared with 416grams of the aforementioned silica coated product in 756 mls. of water,stirred in a reaction vessel and heated to 79° C. The slurry pH isadjusted to 1.5. An aqueous solution containing 8.93 grams of SnCl₄5H₂Ois pumped into the slurry over a 2 hour period while maintaining the pHat 1.5 with 10% Na₂CO₃ solution. After the addition is complete, theslurry temperature is raised to 82° C. and the pH adjusted to 3.0 with10% Na₂CO₃ solution. An aqueous 39% FeCl₃ solution is pumped in at 0.4g/min while controlling the pH at 3.0 with 10% Na₂CO₃ solution. Theaddition is stopped after 81.8 grams of the iron solution is added, andthe slurry is vacuum-filtered, the presscake washed with water, andcalcined for 90 minutes at 650° C.

Both the calcined product and base iron oxide-coated glass flake arecompared as drawdowns of 12% powder in nitrocellulose lacquer. Thecalcined product is seen to exhibit a bronze shade with superiorreflectivity and chromaticity to that of the base material.

EXAMPLE 5

The following samples with non-zero layers represent computersimulations on the specific pigments described employing a 1 micronthick glass substrate. Samples with zero thicknesses for the silicalayer and second TiO₂ layer are simulations of singly coated commercialpigments and serve as comparisons to the inventive samples. Samples 1and 3 represent pigments that were prepared as described above. Theactual properties measured and observed agreed with the simulatedproperties. TABLE 1 Second First TiO₂ Silica TiO₂ Sample Target Layer,Layer, Layer, No. Color Nm¹ Nm¹ Nm¹ L* a* b* 1 White 62 80 57 90.6 −2.60.2 2 White 62 0 0 75.5 0.6 0.4 3 Yellow 62 80 87 84.2 −1.2 54.0 4Yellow 87 0 0 64.3 5.2 37.6 5 Yellow² 69 113 69 84.3 −4.0 67.5 6 Red 6280 101 74.7 33.5 −0.7 7 Red 101 0 0 51.4 28.3 0.1 8 Violet 62 40 12957.1 54.0 −53.3 9 Violet 111 0 0 44.6 36.2 −36.7 10 Blue 62 40 144 59.01.1 −56.3 11 Blue 128 0 0 51.7 −0.3 −45.4 12 Green 62 40 172 78.1 −44.20.5 13 Green 157 0 0 70.9 −19.1 −0.5 14 Green² 155 254 155 72.1 −58.8−1.2¹±5 nm²¼ wave pigmentsThe L*, a* and b* data are for normal incidence and specular reflection.

EXAMPLE 6

The following data represent computer simulations on the specificpigments optimized with respect to C* magnitude and employing a 1 micronthick glass substrate. All samples represent pigments that were preparedby the sol-gel technique as described above. The actual propertiesmeasured and observed agreed with the simulated properties. TABLE 2Silica Second Sample Target First TiO₂ Layer, TiO₂ Layer, No. ColorLayer, Nm¹ Nm¹ Nm¹ 0° L* 0° a* 0° b* 0° C.* 1 Yellow 85 80 85 81.0 1.083.0 83.0 2 Yellow 85 40 95 80.0 −3.0 75.0 75.1 3 Orange 102 40 102 64.032.0 34.0 46.7 4 Red 102 40 112 53.0 50.0 1.0 50.0 5 Violet 113 80 11543.2 66.1 −24.9 70.6 6 Blue 60 40 30 47.0 3.0 −60.0 60.1 7 Blue 50 40 3649.3 2.7 −59.2 59.3¹±5 nm

EXAMPLE 7

The following data represent computer simulations on specific pigmentsemploying a 1 micron thick glass substrate. TABLE 3 First Second TiO₂Silica TiO₂ Normal Layer, Layer, Layer, Color Nm¹ Nm¹ Nm¹ 0° L* 0° a* 0°b* 0° C.* White 56 80 56 90.7 −6.0 −0.2 6.00 White 56 78 57 90.7 −6.2−0.1 6.20 White 56 76 58 90.7 −6.6 −0.1 6.60 White 56 74 59 90.6 −6.90.03 6.90 White 56 72 60 90.5 −7.2 0.13 7.20 White 56 70 60 90.3 −7.7−0.33 7.71 White 56 68 61 90.1 −7.9 −0.27 7.91 White 56 66 62 89.9 −8.2−0.24 8.20 White 60 40 65 86.0 −10.0 −1.0 10.0 Yellow 85 78 86 80.4 0.7884.7 84.7 Yellow 85 76 87 80.2 1.15 85.7 85.7 Yellow 85 74 87 80.2 0.7386.1 86.1 Yellow 85 72 88 80.3 0.35 86.2 86.2 Yellow 85 70 89 80.0 0.9785.8 85.8 Yellow 85 68 89 80.0 0.70 85.5 85.5 Yellow 85 66 90 80.0 0.4785.0 85.0 Red 102 80 104 49.0 57.0 3.0 57.1 Red 205 80 205 75.0 43.0 6.043.4 Violet 156 40 28 42.0 61.0 −64.0 88.4 Violet 60 40 19 31.0 55.0−56.0 78.5 Violet 35 40 30 33.0 54.0 −51.0 74.3 Violet 40 40 30 30.060.0 −67.0 89.9 Violet 45 40 27 27.0 67.0 −71.0 97.6 Violet 111 80 11138.0 71.0 −51.0 87.4 Blue 55 40 33 48.3 2.6 −60.3 60.4 Green 157 80 15777.8 −59.8 0.2 59.8 Green 156 40 175 71.0 −45.0 −2.0 45.0¹±5 nm

EXAMPLE 8

The pigment of this invention can be formulated into a powder eye shadowby thoroughly blending and dispersing the following materials:Ingredients Wt. Parts Mearltalc TCA ® (Talc) 18 Mearlmica ® SVA (Mica)20 Magnesium Myristate 5 Silica 2 CLOISONNE ® Red 424C (Red TiO₂-coatedmica) 20 CLOISONNE ® Violet 525C (Violet TiO₂-coated mica) 13CLOISONNE ® Nu-Antique Blue 626CB (TiO₂-coated 2 mica/iron oxide-coatedmica) CLOISONNE ® Cerise Flambe 550Z 2 (iron oxide-coated mica)Preservatives & Antioxidant q.s.

Then 7 parts of octyl palmitate and 1 part of isostearyl neopentanoateare heated and mixed until uniform, at which time the resulting mixtureis sprayed into the dispersion and the blending continued. The blendedmaterial is pulverized and then 5 parts of Cloisonne Red 424C and 5parts of the pigment of this invention added and mixed until a uniformpowder eye shadow is obtained.

EXAMPLE 9

The pigment can be formulated into a lipstick by placing the followingamounts of the listed ingredients into a heated vessel and raising thetemperature to 85.+−0.3° C.: Ingredients Wt. Parts Candelilla Wax 2.75Carnauba Wax 1.25 Beeswax 1.00 Ceresine Wax 5.90 Ozokerite Wax 6.75Microcrystalline Wax 1.40 Oleyl Alcohol 3.00 Isostearyl Palmitate 7.50Isostearyl Isostearate 5.00 Caprylic/Capric Triglyceride 5.00Bis-Diglycerylpolyalcohol Adipate 2.00 Acetylated Lanolin Alcohol 2.50Sorbitan Tristearate 2.00 Aloe Vera 1.00 Castor Oil 37.50 Red 6 Lake0.25 Tocopheryl Acetate 0.20 Phenoxyethanol, Isopropylparaben, 1.00 andbutylparaben Antioxidant q.s.

A mixture of 13 parts of the pigment of this invention and 1 part ofkaolin are added and mixed until all of the pigment is well dispersed.Fragrance is added as desired and mixed with stirring. The resultingmixture is poured into molds at 75.+−0.5° C., allowed to cool and flamedinto lipsticks.

Various changes and modifications can be made in the present inventionwithout departing from the spirit and scope thereof. The variousembodiments which were illustrated herein were set forth in order toillustrate the invention but were not intended to limit it.

1. A multilayer effect pigment comprising: a transparent substratehaving a first layer of titanium dioxide thereon, said first layerhaving a thickness of about 35 to 160 nm, a second layer of a lowrefractive index material on said first layer and an outermost layer ofa high refractive index material placed on said second layer, said highrefractive index material comprises titanium dioxide having a thicknessof from about 20 to 175 nm and the low refractive index material issilicon dioxide having a thickness of about 20 to 80 nm, and wherein atleast one layer has an optical thickness which is different from all ofthe other layers, whereby the pigment is not a quarter-wave stack. 2.The multilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 62±5 nm, said second layerof silicon dioxide is 80±5 nm and the outermost titanium dioxide layerhas a thickness of 57±5 nm, said pigment being white.
 3. The multilayereffect pigment of claim 1 wherein said first layer is a titanium dioxidelayer having a thickness of 56±5 nm, said second layer of silicondioxide is 80±5 nm and the outermost titanium dioxide layer has athickness of 56±5 nm, said pigment being white.
 4. The multilayer effectpigment of claim 1 wherein said first layer is a titanium dioxide layerhaving a thickness of 56±5 nm, said second layer of silicon dioxide is72±5 nm and the outermost titanium dioxide layer has a thickness of 60±5nm, said pigment being white.
 5. The multilayer effect pigment of claim1 wherein said first layer is a titanium dioxide layer having athickness of 56±5 nm, said second layer of silicon dioxide is 66±5 nmand the outermost titanium dioxide layer has a thickness of 62±5 nm,said pigment being white.
 6. The multilayer effect pigment of claim 1wherein said first layer is a titanium dioxide layer having a thicknessof 60±5 nm, said second layer of silicon dioxide is 40±5 nm and theoutermost titanium dioxide layer has a thickness of 65±5 nm, saidpigment being white.
 7. The multilayer effect pigment of claim 1 whereinsaid first layer is a titanium dioxide layer having a thickness of 62±5nm, said second layer of silicon dioxide is 80±5 nm and the outermosttitanium dioxide layer has a thickness of 87±5 nm, said pigment beingyellow.
 8. The multilayer effect pigment of claim 1 wherein said firstlayer is a titanium dioxide layer having a thickness of 85±5 nm, saidsecond layer of silicon dioxide is 80±5 mm and the outermost titaniumdioxide layer has a thickness of 85±5 mm, said pigment being yellow. 9.The multilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 85±5 mm, said second layerof silicon dioxide having a thickness of 72±5 mm, and said outermostlayer is a titanium dioxide layer having a thickness of 88±5, saidpigment being yellow.
 10. The multilayer effect pigment of claim 1wherein said first layer is a titanium dioxide layer having a thicknessof 85±5 mm, said second layer of silicon dioxide having a thickness of66±5 mm, and said outermost layer is a titanium dioxide layer having athickness of 90±5, said pigment being yellow.
 11. The multilayer effectpigment of claim 1 wherein said first layer is a titanium dioxide layerhaving a thickness of 85±5 nm, said second layer of silicon dioxidehaving a thickness of 40±5 mm, and said outermost layer is a titaniumdioxide layer having a thickness of 95±5, said pigment being yellow. 12.The multilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 102±5 μm, said second layerof silicon dioxide having a thickness of 40±5 nm, and said outermostlayer is a titanium dioxide layer having a thickness of 102±5, saidpigment being orange.
 13. The multilayer effect pigment of claim 1wherein said first layer is a titanium dioxide layer having a thicknessof 102±5 nm, said second layer of silicon dioxide having a thickness of40±5 μm, and said outermost layer is a titanium dioxide layer having athickness of 112±5, said pigment being red.
 14. The multilayer effectpigment of claim 1 wherein said first layer is a titanium dioxide layerhaving a thickness of 62±5 nm, said second layer of silicon dioxide is80±5 nm and the outermost titanium dioxide layer has a thickness of101±5 nm, said pigment being red.
 15. The multilayer effect pigment ofclaim 1 wherein said first layer is a titanium dioxide layer having athickness of 102±5 nm, said second layer of silicon dioxide is 80±5 nmand the outermost titanium dioxide layer has a thickness of 104±5 nm,said pigment being red.
 16. The multilayer effect pigment of claim 1wherein said first layer is a titanium dioxide layer having a thicknessof 62±5 nm, said second layer of silicon dioxide is 40±5 nm and theoutermost titanium dioxide layer has a thickness of 129±5 nm, saidpigment being violet.
 17. The multilayer effect pigment of claim 1wherein said first layer is a titanium dioxide layer having a thicknessof 113±5 nm, said second layer of silicon dioxide having a thickness of80±5 nm, and said outermost layer is a titanium dioxide layer having athickness of 115±5, said pigment being violet.
 18. The multilayer effectpigment of claim 1 wherein said first layer is a titanium dioxide layerhaving a thickness of 156±5 nm, said second layer of silicon dioxidehaving a thickness of 40±5 nm, and said outermost layer is a titaniumdioxide layer having a thickness of 28±5, said pigment being violet. 19.The multilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 60±5 nm, said second layerof silicon dioxide having a thickness of 40±5 nm, and said outermostlayer is a titanium dioxide layer having a thickness of 19±5, saidpigment being violet.
 20. The multilayer effect pigment of claim 1wherein said first layer is a titanium dioxide layer having a thicknessof 35±5 nm, said second layer of silicon dioxide having a thickness of40±5 nm, and said outermost layer is a titanium dioxide layer having athickness of 30±5, said pigment being violet.
 21. The multilayer effectpigment of claim 1 wherein said first layer is a titanium dioxide layerhaving a thickness of 45±5 nm, said second layer of silicon dioxidehaving a thickness of 40±5 nm, and said outermost layer is a titaniumdioxide layer having a thickness of 27±5, said pigment being violet. 22.The multilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 111±5 nm, said second layerof silicon dioxide having a thickness of 80±5 nm, and said outermostlayer is a titanium dioxide layer having a thickness of 111±5, saidpigment being violet.
 23. The multilayer effect pigment of claim 1wherein said first layer is a titanium dioxide layer having a thicknessof 62±5 nm, said second layer of silicon dioxide is 40±5 mm and theoutermost titanium dioxide layer has a thickness of 144±5 nm, saidpigment being blue.
 24. The multilayer effect pigment of claim 1 whereinsaid first layer is a titanium dioxide layer having a thickness of 60±5nm, said second layer of silicon dioxide having a thickness of 40±5 nm,and said outermost layer is a titanium dioxide layer having a thicknessof 30±5, said pigment being blue.
 25. The multilayer effect pigment ofclaim 1 wherein said first layer is a titanium dioxide layer having athickness of 50±5 mm, said second layer of silicon dioxide having athickness of 40±5 nm, and said outermost layer is a titanium dioxidelayer having a thickness of 36±5, said pigment being blue.
 26. Themultilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 62±5 nm, said second layerof silicon dioxide is 40±5 nm and the outermost titanium dioxide layerhas a thickness of 172±5 mm, said pigment being green.
 27. Themultilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 157±5 mm, said second layerof silicon dioxide is 80±5 nm and the outermost titanium dioxide layerhas a thickness of 157±5 mm, said pigment being green.
 28. Themultilayer effect pigment of claim 1 wherein said first layer is atitanium dioxide layer having a thickness of 156±5 mm, said second layerof silicon dioxide is 40±5 nm and the outermost titanium dioxide layerhas a thickness of 175±5 nm, said pigment being green.
 29. A multilayereffect pigment comprising: a transparent substrate having a first layerof titanium dioxide thereon, said first layer having a thickness of205±5 nm; a second layer of silicon dioxide on said first layer, saidsecond layer of silicon dioxide having a thickness of 80±5 nm; and anoutermost titanium dioxide layer placed on said second layer and havinga thickness of 205±5 mm, said pigment being red.